Method of forming a nitrogen-enriched region within silicon-oxide-containing masses

ABSTRACT

The invention encompasses a method of incorporating nitrogen into a silicon-oxide-containing layer. The silicon-oxide-containing layer is exposed to a nitrogen-containing plasma to introduce nitrogen into the layer. The nitrogen is subsequently thermally annealed within the layer to bond at least some of the nitrogen to silicon within the layer. The invention also encompasses a method of forming a transistor. A gate oxide layer is formed over a semiconductive substrate. The gate oxide layer comprises silicon dioxide. The gate oxide layer is exposed to a nitrogen-containing plasma to introduce nitrogen into the layer, and the layer is maintained at less than or equal to 400° C. during the exposing. Subsequently, the nitrogen within the layer is thermally annealed to bond at least a majority of the nitrogen to silicon. At least one conductive layer is formed over the gate oxide layer. Source/drain regions are formed within the semiconductive substrate, and are gatedly connected to one another by the at least one conductive layer. The invention also encompasses transistor structures.

This patent resulted from a continuation of U.S. patent application Ser.No. 10/050,373, which was filed on Jan. 15, 2002 now U.S. Pat. No.7,432,166, and which is hereby incorporated herein by reference; whichresulted from a divisional of U.S. patent application Ser. No.09/633,556, which was filed on Aug. 7, 2000, now U.S. Pat. No. 6,660,657B1, and which is hereby incorporated herein by reference.

TECHNICAL FIELD

The invention pertains to methods of incorporating nitrogen intosilicon-oxide-containing layers, and in particular application pertainsto methods of forming transistors. The invention also pertains totransistor structures.

BACKGROUND OF THE INVENTION

It can be desirable to incorporate nitrogen intosilicon-oxide-containing layers during formation of semiconductordevices. For instance, it can be desirable to incorporate nitrogen intogate oxides (which typically are silicon dioxide) to reduce dopantpenetration through the oxides. Methods have been developed whereinnitrogen is incorporated into a gate oxide during deposition of the gateoxide by including nitrogen species amongst the deposited materials. Itcan, however, be difficult to control nitrogen location withinsilicon-oxide-containing layers formed by such techniques. Accordingly,it would be desirable to develop alternative techniques forincorporating nitrogen into silicon-oxide-containing layers.

SUMMARY OF THE INVENTION

In one aspect, the invention encompasses a method of incorporatingnitrogen into a silicon-oxide-containing layer. Thesilicon-oxide-containing layer is exposed to a nitrogen-containingplasma to introduce nitrogen into the layer. The nitrogen issubsequently thermally annealed within the layer to bond at least someof the nitrogen to silicon within the layer.

In another aspect, the invention encompasses a method of forming atransistor. A gate oxide layer is formed over a semiconductivesubstrate. The gate oxide layer comprises silicon dioxide. The gateoxide layer is exposed to a nitrogen-containing plasma to introducenitrogen into the layer, and the layer is maintained at less than orequal to 400° C. during the exposing. Subsequently, the nitrogen withinthe layer is thermally annealed to bond at least a majority of thenitrogen to silicon. At least one conductive layer is formed over thegate oxide layer. Source/drain regions are formed within thesemiconductive substrate, and are gatedly connected to one another bythe at least one conductive layer.

In yet another aspect, the invention encompasses transistor structures.

BRIEF DESCRIPTION OF THE DRAWINGS

Preferred embodiments of the invention are described below withreference to the following accompanying drawings.

FIG. 1 is a diagrammatic, cross-sectional view of a semiconductor waferfragment at an initial processing step of a method of the presentinvention.

FIG. 2 is a view of the FIG. 1 wafer fragment shown at a processing stepsubsequent to that of FIG. 1.

FIG. 3 is a view of the FIG. 1 wafer fragment shown at a processing stepsubsequent to that of FIG. 2.

FIG. 4 is a view of the FIG. 1 wafer fragment shown at a processing stepsubsequent to that of FIG. 3.

FIG. 5 is a view of the FIG. 1 wafer fragment shown at a processing stepsubsequent to that of FIG. 4.

FIG. 6 is a view of the FIG. 1 wafer fragment shown at a processing stepsubsequent to that of FIG. 5.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

This disclosure of the invention is submitted in furtherance of theconstitutional purposes of the U.S. Patent Laws “to promote the progressof science and useful arts” (Article 1, Section 8).

A method of the present invention is described with reference to FIGS.1-6. Referring initially to FIG. 1, a semiconductor wafer fragment 10comprises a substrate 12 having a silicon-oxide-containing layer 14formed thereover. Substrate 12 can comprise, for example,monocrystalline silicon lightly-doped with a background p-type dopant.To aid in interpretation of the claims that follow, the terms“semiconductive substrate” and “semiconductor substrate” are defined tomean any construction comprising semiconductive material, including, butnot limited to, bulk semiconductive materials such as a semiconductivewafer (either alone or in assemblies comprising other materialsthereon), and semiconductive material layers (either alone or inassemblies comprising other materials). The term “substrate” refers toany supporting structure, including, but not limited to, thesemiconductive substrates described above.

Silicon-oxide-containing layer 14 can comprise, for example, anymaterial comprising silicon oxide, including, for example, silicondioxide, borophosphosilicate glass (BPSG), etc. In a particularembodiment of the present invention, layer 14 comprises silicon dioxide,and is ultimately utilized as a gate oxide layer in a transistorstructure. In such embodiment, layer 14 can have a thickness of fromabout 5Å to about 60Å. Oxide layer 14 has a lower surface 15 onsubstrate 12 and an upper surface 17 above substrate 12 and opposingsurface 15.

Referring next to FIG. 2, oxide-containing layer 14 has nitrogen (shownin FIG. 2 as “N”) implanted therein. The nitrogen within layer 14 isshown by stippling, and a dashed line 16 is shown to indicate alowermost boundary of the implanted nitrogen. A predominant portion ofthe implanted nitrogen is preferably within an upper half of oxide layer14, and more preferably within an upper third of oxide layer 14. Inparticular embodiments, an entirety of the implanted nitrogen is in anupper half of oxide layer 14, and the entirety of the implanted nitrogencan be in an upper third of oxide layer 14, the upper fourth of layer14, or the upper fifth of layer 14, for example.

An exemplary method of providing nitrogen within oxide layer 14 is toexpose layer 14 to activated nitrogen from a nitrogen-containing plasmaand thereby introduce nitrogen into layer 14, with the term “activated”indicating that the nitrogen species is different than the form ofnitrogen fed to the plasma. An activated nitrogen species can comprise,for example, a nitrogen ion or a nitrogen atom in an energy state higherthan its ground state. Introduction of nitrogen into layer 14 forms anitrogen-enriched upper region 18 of layer 14 and anon-nitrogen-enriched region 20 beneath region 18.

The nitrogen-containing plasma can be formed from, for example, N₂, NH₃and/or N₂O. The plasma can be predominantly composed ofnitrogen-containing species, consist essentially of nitrogen-containingspecies, or consist entirely of nitrogen-containing species. Inexemplary embodiments, layer 14 is maintained at a temperature of lessthan or equal to 400° C. during the exposure to the nitrogen-containingplasma. Such can alleviate diffusion of nitrogen into a lower half ofoxide layer 14. Particular exemplary temperatures can be from 50° C. to400° C., with a suitable temperature being about 65° C. Thenitrogen-containing plasma can be maintained with a power of from about500 watts to about 5,000 watts during exposure of layer 14 to theplasma, and in particular embodiments can be maintained with a power offrom about 500 watts to about 3,000 watts during the exposing. Apressure within a reaction chamber comprising the plasma and oxide layer14 can be less than about 3 Torr, and can be, for example, from about 5mTorr to about 10 mTorr. The time of exposure of layer 14 to thenitrogen-containing plasma is preferably for a time of less than orequal to about 1 minute, and in particular embodiments can be for a timeof from about 3 seconds to about 1 minute. An exemplary process utilizesan exposure time of from about 10 seconds to about 15 seconds.

Referring to FIG. 3, layer 14 is exposed to an annealing temperaturewhich causes at least some of the nitrogen within region 18 to bond tosilicon proximate the nitrogen and accordingly form Si—N bonds whichretain the nitrogen within layer 14. The annealing can comprise thermalprocessing at a temperature of less than 1,100° C. for a time of atleast 3 seconds, and can comprise, for example, a temperature of 700° C.for a time of about 30 seconds, or 1,050° C. for a time of about 5seconds. Alternatively, the annealing can comprise rapid thermalprocessing (RTP) utilizing a ramp rate of at least 50° C./second to atemperature of less than 1,000° C., with such temperature beingmaintained for at least about 30 seconds. Suitable processing caninclude a temperature of about 900° C. for a time of about 60 seconds.

Preferably, a predominant portion of the nitrogen within layer 14 isbonded to silicon of the layer during the annealing, and morepreferably, all of the nitrogen within layer 14 is bonded to siliconduring the annealing. The bonded nitrogen is precluded from migratingdownwardly into layer 14, and accordingly is locked into region 18. Inexemplary embodiments, the nitrogen does not migrate below an upper halfof oxide region 14 during the annealing, and accordingly, the nitrogenpreferably remains within an upper half of layer 14 after the annealing.In other exemplary embodiments, the nitrogen does not migrate below anupper third of layer 14 during the annealing, and accordingly isretained in an upper third of layer 14 after the annealing.Additionally, an entirety of the nitrogen can be in upper fourth oflayer 14 after the annealing, or in an upper fifth of layer 14 after theannealing. In particular embodiments of the invention, there is nomeasurable nitrogen below the top 50% of layer 14, and in exemplaryembodiments there is no measurable nitrogen below the top 10 Å of layer14.

A reason for which it is desired to keep nitrogen in an upper half, ormore preferably an upper third, of layer 14 is to alleviate anypossibility that nitrogen will migrate through layer 14 and to an uppersurface of substrate 12. If nitrogen should reach the upper surface ofsubstrate 12, such can effectively alter a dopant concentration withinthe effected region of substrate 12, and change electricalcharacteristics of devices ultimately formed over substrate 12. Forinstance, if oxide layer 14 is ultimately utilized as a gate oxide, thenthe region of substrate 12 beneath oxide layer 14 will be a channelregion of a transistor gate. If nitrogen migrates through layer 14 andinto the channel region, such can affect a threshold voltage of atransistor device, and destroy the device for its intended purpose.

Referring to FIG. 4, a stack 30 is formed over layer 14. Stack 30comprises materials which are ultimately to be patterned into atransistor gate, and accordingly comprises at least one conductivelayer. In the shown embodiment, stack 30 comprises two conductivelayers, and specifically comprises conductive layers 32 and 34. Stack 30further comprises an insulative layer 36 formed over conductive layers32 and 34. Conductive layer 32 can comprise, for example,conductively-doped silicon such as, for example, conductively-dopedpolysilicon, and can be doped with either n-type or p-typeconductivity-enhancing dopant. Conductive layer 34 can comprise, forexample, a metal silicide, such as, for example, tungsten silicide ortitanium silicide. Insulative layer 36 can comprise, for example,silicon nitride.

If conductive layer 32 comprises conductively-doped silicon, thenitrogen within layer 14 can block migration of dopants from polysilicon32 into substrate 12. Such can alleviate problems which would otherwiseoccur if dopant were to migrate through oxide layer 14 and into thesubstrate 12. Problems which can occur through dopant migration fromconductively doped layer 32 into substrate 12 are similar to theproblems discussed above which can occur if nitrogen migrates fromregion 18 of oxide layer 14 into substrate 12, and correspond toproblems associated with undesired doping of a channel region formed insubstrate 12. Such problems can be particularly severe if p-type dopedpolysilicon is utilized as a conductive material in forming a PMOSdevice.

Referring to FIG. 5, oxide layer 14 and stack 30 are patterned into atransistor gate structure 40. Such patterning can be accomplished by,for example, photolithographic processing wherein a masking layer (suchas photoresist) is formed over stack 30 and a pattern is transferredfrom the patterned masking layer to stack 30 and oxide 14. The maskinglayer (not shown) can then be removed after transfer of the pattern tolead to resulting structure 40. It is noted that although oxide layer 14is shown patterned together with stack 30, the invention encompassesother embodiments wherein only stack 30 is patterned.

Lightly doped diffusion (Ldd) regions 42 are shown formed adjacentstructure 40, and can be formed by, for example, implanting aconductivity-enhancing dopant into substrate 12 after forming patternedgate structure 40. Regions 42 can comprise one or both of either n-typeconductivity-enhancing dopant or p-type conductivity-enhancing dopant,depending on the type of transistor device which is ultimately to beformed, (i.e., depending on whether the device is to be a PMOStransistor or an NMOS transistor).

Referring to FIG. 6, sidewalls 44 are shown formed adjacent gatestructure 40. Sidewalls 44 typically comprise an insulative material,and can comprise, for example, silicon dioxide or silicon nitride.Sidewalls 44 can be formed by, for example, forming a layer of materialover substrate 12 and structure 40, and subsequently anisotropicallyetching the layer of material to leave sidewall spacers 44 alongsidewalls of structure 40.

Source/drain regions 46 are shown formed within substrate 12 andadjacent lightly doped diffusion regions 42. Source/drain regions 46 canbe formed by, for example, implanting conductivity-enhancing dopant intosubstrate 12 after formation of sidewall spacers 44. Source/drainregions 46 are preferably heavily-doped (i.e., doped to a concentrationof greater than 1×10¹⁹ atoms/cm³) with conductivity-enhancing dopant.The conductivity-enhancing dopant can be either n-type or p-typedepending on the type of transistor device which is ultimately to beformed.

Gate structure 40, together with regions 42 and 46, defines a fieldeffect transistor. A channel region 48 of such transistor is defined tobe beneath oxide layer 14. Structure 40 can be utilized to controlchannel region 48 so as to gatedly connect a source/drain region on oneside of gate 40 with a source/drain region on other side of gate 40.

It is noted that the structures of FIGS. 4-6 are not drawn to scale, andspecifically that layer 14 is shown much larger in proportion to layers32, 34 and 36 than would typically occur in actual structures. Layer 14is shown in such proportion to permit the portions 18 and 20 of layer 14to be clearly illustrated in the drawings.

In compliance with the statute, the invention has been described inlanguage more or less specific as to structural and methodical features.It is to be understood, however, that the invention is not limited tothe specific features shown and described, since the means hereindisclosed comprise preferred forms of putting the invention into effect.The invention is, therefore, claimed in any of its forms ormodifications within the proper scope of the appended claimsappropriately interpreted in accordance with the doctrine ofequivalents.

1. A method of forming a nitrogen-enriched region within asilicon-oxide-containing mass, comprising: providing thesilicon-oxide-containing mass over a substrate; thesilicon-oxide-containing mass having a bare upper surface extending to alower surface in physical contact with the substrate; forming anitrogen-enriched region within an upper third of the mass; and afterforming the nitrogen-enriched region, thermally annealing the nitrogenwithin the nitrogen-enriched region, while the bare upper surface of thesilicon-oxide-containing mass remains bare, to bond at least some of thenitrogen to silicon proximate the nitrogen; the nitrogen-enriched regionremaining confined to the upper third of the silicon-oxide-containingmass during the annealing.
 2. The method of claim 1 wherein thenitrogen-enriched region is formed only in the upper fourth of the massand remains confined to the upper fourth of the mass during theannealing.
 3. The method of claim 1 wherein the nitrogen-enriched regionis formed only in the upper fifth of the mass by the exposing andremains confined to the upper fifth of the mass during the annealing. 4.The method of claim 1 wherein the mass has a thickness of no greaterthan about 60 Å.
 5. The method of claim 1 wherein the mass has athickness of from between about 5Å and 60 Å.
 6. The method of claim 1wherein the annealing comprises thermal processing at a temperature ofabout 700° C. for a time of about 30 seconds.
 7. The method of claim 1wherein the annealing comprises thermal processing at a temperature ofabout 1050° C. for a time of about 5 seconds.
 8. The method of claim 1wherein the annealing comprises rapid thermal processing at a ramp rateof at least about 50° C./sec to a process temperature of less than 1000°C., with the process temperature being maintained for at least about 30seconds.
 9. The method of claim 1 further comprising forming aconductive mass upon the upper surface of the silicon-oxide-containingmass.
 10. The method of claim 1 wherein the silicon-oxide-containingmass comprises silicon dioxide.
 11. The method of claim 1 wherein thesilicon-oxide-containing mass comprises borophosphosilicate glass.